Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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TITLE
METHODS FOR PROCESSING AUSTENITIC ALLOYS
INVENTORS
Robin M. Forbes Jones
Erin T. McDevitt
BACKGROUND OF THE TECHNOLOGY
FIELD OF THE TECHNOLOGY
[0001] The present disclosure relates to methods of alloys. The
present methods may find application in, for example, and without limitation,
the chemical, mining, oil, and gas industries.
DESCRIPTION OF THE BACKGROUND OF THE TECHNOLOGY
[0002] Metal alloy parts used in chemical processing facilities may be
in contact with highly corrosive and/or erosive compounds under demanding
conditions. These conditions may subject metal alloy parts to high stresses
and aggressively promote corrosion and erosion, for example. If it is
necessary to replace damaged, worn, or corroded metallic parts of chemical
processing equipment, it may be necessary to suspend facility operations for
a period of time. Therefore, extending the useful service life of metal alloy
parts used in chemical processing facilities can reduce product cost. Service
life may be extended, for example, by improving mechanical properties and/or
corrosion resistance of the alloys.
[0003] Similarly, in oil and gas drilling operations, drill string
components may degrade due to mechanical, chemical, and/or environmental
conditions. The drill string components may be subject to impact, abrasion,
friction, heat, wear, erosion, corrosion, and/or deposits. Conventional alloys
may suffer from one or more limitations that impact their utility as drill
string
components. For example, conventional materials may lack sufficient
mechanical properties (for example, yield strength, tensile strength, and/or
fatigue strength), possess insufficient corrosion
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resistance (for example, pitting resistance and/or stress corrosion cracking),
or lack
necessary non-magnetic properties. Also, the properties of conventional alloys
may
limit the possible size and shape of the drill string components made from the
alloys.
These limitations may reduce the useful life of the components, complicating
and
increasing the cost of oil and gas drilling.
[0004] High strength non-magnetic stainless steels often contain
intermetallic precipitates that decrease the corrosion resistance of the
alloys.
Galvanic corrosion cells that develop between the intermetallic precipitates
and the
base alloy can significantly decrease the corrosion resistance of high
strength non-
magnetic stainless steel alloys used in oil and gas drilling operations.
[0005] The broad chemical composition of one high strength non-magnetic
austenitic stainless steel intended for exploration and production drilling
applications
in the oil and gas industry is disclosed in co-pending U.S. Patent Application
Serial
No. 13/331,135, filed on December 20, 2011. It was discovered that the
microstructures of forged workpieces of certain of the steels described in the
1135
application can include intermetallic precipitates. It is believed that the
intermetallic
precipitates are a-phase precipitates, comprised of Fe-Cr-Ni intermetallic
compounds. The a-phase precipitates may impair the corrosion resistance of the
stainless steels disclosed in the '135 application, which may adversely affect
the
suitability of the steels for use in certain aggressive drilling environments.
SUMMARY
[0006] According to one non-limiting aspect of the present disclosure, a
method of processing a workpiece to inhibit precipitation of intermetallic
compounds
comprises at least one of thermomechanically working and cooling a workpiece
including an austenitic alloy. During the at least one of thermomechanically
working
and cooling the workpiece, the austenitic alloy is at temperatures in a
temperature
range spanning a temperature just less than a calculated sigma solvus
temperature
of the austenitic alloy down to a cooling temperature for a time period no
greater
than a critical cooling time. The calculated sigma solvus temperature is a
function of
the composition of the austenitic alloy in
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weight percentages and is equal to 1155.8 - (760.4).(nickel/iron) +
(1409).(chromium/iron) + (2391.6).(molybdenum/iron) - (288.9)-(manganese/iron)
-
(634.8).(cobalt/iron) + (107.8).(tungsten/iron). The cooling temperature is a
function
of the composition of the austenitic alloy in weight percentages and is equal
to
1290.7 - (604.2).(nickel/iron) + (829.5).(chromium/iron) +
(1899.6)-(molybdenumiiron) - (635.5).(cobalt/iron) + (1251.3).(tungsten/iron).
The
critical cooling time is a function of the composition of the austenitic alloy
in weight
percentages and is equal to in log10 2.948 + (3.631).(nickel/iron) -
(4.846).(chromium/iron) - (11.157)-(molybdenum/iron) + (3.457).(cobalt/iron)
(6.74)-(tungsten/iron).
[0007] In certain non-limiting embodiments of the method,
thermomechanically working the workpiece comprises forging the workpiece. Such
forging may comprise, for example, at least one of roll forging, swaging,
cogging,
open-die forging, impression-die forging, press forging, automatic hot
forging, radial
forging, and upset forging. In certain non-limiting embodiments of the method,
the
critical cooling time is in a range of 10 minutes to 30 minutes, greater than
10
minutes, or greater than 30 minutes.
[0008] In certain non-limiting embodiments of the method, after at least
one of thermomechanically working and cooling the workpiece, the workpiece is
heated to an annealing temperature that is at least as great as the calculated
sigma
solvus temperature, and holding the workpiece at the annealing temperature for
a
period of time sufficient to anneal the workpiece. As the workpiece cools from
the
annealing temperature, the austenitic alloy is at temperatures in a
temperature
range spanning a temperature just less than the calculated sigma solvus
temperature down to the cooling temperature for a time no greater than the
critical
cooling time.
[0009] According to another non-limiting aspect of the present disclosure, a
method of processing an austenitic alloy workpiece to inhibit precipitation of
intermetallic compounds comprises forging the workpiece, cooling the forged
workpiece, and, optionally, annealing the cooled workpiece. During forging the
workpiece and cooling the forged workpiece, the austenitic alloy cools through
a
temperature range spanning a temperature just less than a calculated sigma
solvus
temperature of the austenitic alloy down to a cooling temperature for a time
no
3
greater than a critical cooling time. The calculated sigma solvus temperature
is a function of the composition of the austenitic alloy in weight percentages
and is equal to 1155.8- (760.4).(nickel/iron) + (1409)-(chromium/iron) +
(2391.6)=(molybdenum/iron) - (288.9)=(manganese/iron) - (634.8)=(cobalt/iron)
+ (107.8)=(tungsten/iron). The cooling temperature is a function of the
composition of the austenitic alloy in weight percentages and is equal to
1290.7 - (604.2).(nickel/iron) + (829.6).(chromium/iron) +
(1899.6)-(molybdenumnron) - (635.5)=(cobalt/iron) + (1251.3)=(tungsten/iron).
The critical cooling time is a function of the composition of the austenitic
alloy
in weight percentages and is equal to in logio 2.948 + (3.631)-(nickel/iron) -
(4.846).(chromium/iron) -(11. 57)-(molybdenum/iron) + (3.457)-(cobalt/iron) -
(6.74).(tungsten/iron). In certain non-limiting embodiments, forging the
workpiece comprises at least one of roll forging, swaging, cogging, open-die
forging, impression-die forging, press forging, automatic hot forging, radial
forging, and upset forging.
[009a] In yet another aspect, the present invention provides a method of
processing a workpiece to inhibit precipitation of intermetallic compounds,
the
method comprising: at least one of thermomechanically working and cooling a
workpiece including an austenitic alloy, wherein during the at least one of
thermomechanically working and cooling the workpiece, the austenitic alloy is
at
temperatures in a temperature range spanning a temperature just less than a
calculated sigma solvus temperature of the austenitic alloy down to a cooling
temperature for a time no greater than a critical cooling time; wherein the
austenitic alloy consists of, in weight percentages based on total alloy
weight,
up to 0.2 carbon, up to 20 manganese, 0.1 to 1.0 silicon, 14.0 to 28.0
chromium, 15.0 to 25.43 nickel, 2.0 to 9.0 molybdenum, 0.1 to 3.0 copper, 0.08
to 0.9 nitrogen, 0.1 to 5.0 tungsten, 0.5 to 5.0 cobalt, up to 1.0 titanium,
up to
0.05 boron, up to 0.05 phosphorus, up to 0.05 sulfur, 0.01 to 1.0 vanadium, 20
to 60 iron, up to 1.0 niobium, up to 1.0 tantalum, up to 1.0 aluminum, up to
0.1
cerium, up to 0.1 lanthanum, up to 0.5 ruthenium, up to 1.0 zirconium, and
incidental impurities; wherein the calculated sigma solvus temperature is a
function of the composition of the austenitic alloy in weight percentages and,
in
Fahrenheit degrees, is equal to
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1155.8-(760.4)=(nickel/iron)+(1409)-(chromium/iron)+(2391.6)=(molybdenum/iro
n)-(288.9)-(manganese/iron)-(634.8).(cobalt/iron)+(107.8).
(tungsten/iron); wherein the cooling temperature is a function of the
composition
of the austenitic alloy in weight percentages and, in Fahrenheit degrees, is
equal to
1290.7-(604.2).(nickel/iron)+(829.6)-(chromiumnron)+(1899.6)-(molybdenum/ir
on)-(635.5).(cobalt/iron)+(1251.3).(tungsten/iron); and wherein the critical
cooling time is a function of the composition of the austenitic alloy in
weight
percentages and, in minutes, is equal to, in logio,
2.948+(3.631)-(nickel/iron)-(4.846)-(chromium/iron)-(11.157)=(molybdenum/iro
n)+(3.457)-(cobalt/iron)-(6.74)-(tungsten/iron), and wherein the critical
cooling
time is in a range of 10 minutes to 30 minutes.
[009b] In yet another aspect, the present invention provides a method of
processing an austenitic alloy workpiece to inhibit precipitation of
intermetallic
compounds, the method comprising: forging the workpiece; cooling the forged
workpiece; and optionally, annealing the cooled workpiece; wherein the
austenitic alloy consists of, in weight percentages based on total alloy
weight,
up to 0.2 carbon, up to 20 manganese, 0.1 to 1.0 silicon, 14.0 to 28.0
chromium, 15.0 to 25.43 nickel, 2.0 to 9.0 molybdenum, 0.1 to 3.0 copper, 0.08
to 0.9 nitrogen, 0.1 to 5.0 tungsten, 0.5 to 5.0 cobalt, up to 1.0 titanium,
up to
0.05 boron, up to 0.05 phosphorus, up to 0.05 sulfur, 0.01 to 1.0 vanadium, 20
to 60 iron, up to 1.0 niobium, up to 1.0 tantalum, up to 1.0 aluminum, up to
0.1
cerium, up to 0.1 lanthanum, up to 0.5 ruthenium, up to 1.0 zirconium, and
incidental impurities; wherein during forging the workpiece and cooling the
forged workpiece the austenitic alloy cools through a temperature range
spanning a temperature just less than a calculated sigma solvus temperature of
the austenitic alloy down to a cooling temperature for a time no greater than
a
critical cooling time; wherein the calculated sigma solvus temperature is a
function of the composition of the austenitic alloy in weight percentages and,
in
Fahrenheit degrees, is equal to
1155.8-(760.4).(nickel/iron) (1409)=(chromium/iron)+
(2391.6).(molybdenum/iron)-(288.9)-(manganesenron)-(634.8)=(cobalt/iron)
+(107.8).(tungsten/iron); wherein the cooling temperature is a function of the
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composition of the austenitic alloy in weight percentages and, in Fahrenheit
degrees, is equal to
1290.7-(604.2)-(nickel/iron)+(829.6)-(chromium/iron)+(1899.6)-(molybdenum/ir
on)-(635.5).(cobalt/iron)+(1251.3)-(tungsten/iron); wherein the critical
cooling
time is a function of the composition of the austenitic alloy in weight
percentages and, in minutes, is equal to, in loglo,
2.948+(3.631)-(nickel/iron)-(4.846).(chromium/iron)-(11.157)-(molybdenumnro
n)+(3.457)-(cobalt/iron)-(6.74).(tungsten/iron), and wherein the critical
cooling
time is in a range of 10 minutes to 30 minutes.
[009c] In yet another aspect, the present invention provides a method of
processing a workpiece to inhibit precipitation of intermetallic compounds,
the
method comprising: at least one of thermomechanically working and cooling a
workpiece including an austenitic alloy, wherein during the at least one of
thermomechanically working and cooling the workpiece, the austenitic alloy is
at
temperatures in a temperature range spanning a temperature just less than a
calculated sigma solvus temperature of the austenitic alloy down to a cooling
temperature for a time no greater than a critical cooling time; wherein the
austenitic alloy consists of, in weight percentages based on total alloy
weight,
up to 0.2 carbon, up to 20 manganese, 0.1 to 1.0 silicon, 14.0 to 28.0
chromium, 15.0 to 32.0 nickel, 2.0 to 9.0 molybdenum, 0.1 to 3.0 copper, 0.08
to 0.9 nitrogen, 0.1 to 5.0 tungsten, 0.5 to 5.0 cobalt, up to 1.0 titanium,
up to
0.05 boron, up to 0.05 phosphorus, up to 0.05 sulfur, 20 to 60 iron, up to 1.0
vanadium, up to 1.0 niobium, up to 1.0 tantalum, up to 1.0 aluminum, up to 0.1
cerium, up to 0.1 lanthanum, up to 0.5 ruthenium, up to 1.0 zirconium, and
incidental impurities; wherein the calculated sigma solvus temperature is a
function of the composition of the austenitic alloy in weight percentages and,
in
Fahrenheit degrees, is equal to
1155.8-(760.4)-(nickel/iron)+(1409).(chromium/iron)+
(2391.6)-(molybdenum/iron)-(288.9).(manganesenron)-(634.8).(cobalt/iron)+
(107.8)-(tungsten/iron); wherein the cooling temperature is a function of the
composition of the austenitic alloy in weight percentages and, in Fahrenheit
degrees, is equal to
1290.7-(604.2).(nickel/iron)+(829.6)=(chromium/iron)+(1899.6).(molybdenum/ir
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on)-(635.5).(cobalt/iron)+(1251.3).(tungsten/iron); and wherein the critical
cooling time is a function of the composition of the austenitic alloy in
weight
percentages and, in minutes, is equal to, in logio,
2.948+(3.631).(nickel/iron)-(4.846).(chromiumnron)-(11.157).(molybdenum/iro
n)+(3.457)=(cobalt/iron)-(6.74).(tungsten/iron), and wherein the critical
cooling
time is in a range of 10 minutes to 30 minutes.
[009d] In yet another aspect, the present invention provides a method of
processing an austenitic alloy workpiece to inhibit precipitation of
intermetallic
compounds, the method comprising: forging the workpiece; cooling the forged
workpiece; and optionally, annealing the cooled workpiece; wherein the
austenitic alloy consist of, in weight percentages based on total alloy
weight, up
to 0.2 carbon, up to 20 manganese, 0.1 to 1.0 silicon, 14.0 to 28.0 chromium,
15.0 to 32.0 nickel, 2.0 to 9.0 molybdenum, 0.1 to 3.0 copper, 0.08 to 0.9
nitrogen, 0.1 to 5.0 tungsten, 0.5 to 5.0 cobalt, up to 1.0 titanium, up to
0.05
boron, up to 0.05 phosphorus, up to 0.05 sulfur, 20 to 60 iron, up to 1.0
vanadium, up to 1.0 niobium, up to 1.0 tantalum, up to 1.0 aluminum, up to 0.1
cerium, up to 0.1 lanthanum, up to 0.5 ruthenium, up to 1.0 zirconium, and
incidental impurities; wherein during forging the workpiece and cooling the
forged workpiece the austenitic alloy cools through a temperature range
spanning a temperature just less than a calculated sigma solvus temperature of
the austenitic alloy down to a cooling temperature for a time no greater than
a
critical cooling time; wherein the calculated sigma solvus temperature is a
function of the composition of the austenitic alloy in weight percentages and,
in
Fahrenheit degrees, is equal to
1155.8-(760.4)=(nickel/iron)+(1409).(chromium/iron)+(2391.6).(molybdenum/iro
n)-(288.9).(manganese/iron)-(634.8).(cobalthron)+(107.8)-(tungsten/iron);
wherein the cooling temperature is a function of the composition of the
austenitic alloy in weight percentages and, in Fahrenheit degrees, is equal to
1290.7-(604.2).(nickel/iron)+(829.6).(chromium/iron)+(1899.6).(molybdenum/ir
on)-(635.5).(cobalt/iron)4-(1251.3).(tungsten/iron); and wherein the critical
cooling time is a function of the composition of the austenitic alloy in
weight
percentages and, in minutes, is equal to, in logio,
2.9484-(3.631).(nickel/iron)-(4.846)=(chromium/iron)-(11.157).(molybdenum/iro
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n)+(3.457)=(cobalt/iron)-(6.74)=(tungsten/iron), and wherein the critical
cooling
time is in a range of 10 minutes to 30 minutes.
[0010] In certain non-limiting embodiments of the method, forging the
workpiece occurs entirely at temperatures greater than the calculated sigma
solvus temperature. In certain other non-limiting embodiments of the method,
forging the workpiece occurs through the calculated sigma solvus
temperature. In certain non-limiting embodiments of the method, the critical
cooling time is in a range of 10 minutes to 30 minutes, greater than 10
minutes, greater than 30 minutes.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] The features and advantages of apparatus and methods
described herein may be better understood by reference to the accompanying
drawings in which:
[0012] FIG. 1 is a micrograph showing deleterious intermetallic
precipitates in the microstructure at the mid radius of a radial forged
workpiece of a nonmagnetic austenitic alloy;
[0013] FIG. 2 is an isothermal transformation curve or ITT curve
predicting the kinetics for 0.1 weight percent a-phase intermetallic
precipitation in an alloy;
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[0014] FIG. 3 is a plot showing calculated center-of-workpiece
temperature, calculated center temperature, calculated surface temperature,
and
actual temperatures derived from the radial forging of experimental workpieces
of
austenitic alloys according to methods of the present disclosure;
[0015] FIG. 4 is a TTT curve, with associated forming and cooling
temperatures and times, according to embodiments of the present disclosure;
[0016] FIG. 5 is a schematic illustration of a non-limiting embodiment of a
process according to the present disclosure for producing forms of specific
diameter of a high strength non-magnetic steel useful for exploration and
production drilling applications in the oil and gas industry;
[0017] FIG. 6 is a TTT diagram for an embodiment of an alloy having a
relatively short critical cooling time as calculated according to an
embodiment of
the present disclosure;
[0018] FIG. 7 is a micrograph of a center region of an as-forged 9-inch
diameter workpiece produced using an actual cooling time greater than the
calculated critical cooling time required to avoid intermetallic precipitation
of sigma
phase according to the present disclosure;
[0019] FIG. 8 is a TTT diagram for an embodiment of an alloy having a
relatively long critical cooling time as calculated according to an embodiment
of the
present disclosure;
[0020] FIG. 9 is a micrograph showing the microstructure of the mid-radius
of an as-forged 9-inch diameter workpiece using an actual cooling time less
than
the calculated critical cooling time to avoid intermetallic precipitation of
sigma
phase according to the present disclosure;
[0021] FIG. 10 is a plot of temperature versus distance from the back wall
of a gradient furnace for heat treatments used in Example 3 of the present
disclosure;
[0022] FIG. 11 is a TTT diagram plotting sampling temperature gradients
(horizontal lines) and critical cooling times (vertical lines) used in Example
3 of the
present disclosure;
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[0023] FIG. 12 is a figure superimposing microstructures from samples
held for 12 minutes at various temperatures on a TTT diagram for Example 3 of
the
present disclosure;
[0024] FIG. 13 is a figure superimposing microstructures for samples held
at 1080 F for various times on a TTT diagram for Example 3 of the present
disclosure;
[0025] FIG. 14A is a micrograph showing the microstructure of a surface
region of an alloy of Example 4 of the present disclosure that was annealed
and
cooled within the calculated critical cooling time according to the present
disclosure
and is devoid of sigma phase precipitates;
[0026] FIG. 14B is a micrograph showing the microstructure at a center
region of an alloy of Example 4 of the present disclosure that was annealed
but did
not cool within the calculated critical cooling time according to the present
disclosure and exhibits sigma phase precipitates;
[0027] FIG. 15A is a micrograph showing the microstructure of a surface
region of an alloy of Example 5 of the present disclosure that was forged and
cooled within the calculated critical cooling time according to the present
disclosure
and is devoid of sigma phase precipitates;
[0028] FIG. 15B is a micrograph showing the microstructure at a center
region of an alloy of Example 5 of the present disclosure that was forged and
cooled within the calculated critical cooling time according to the present
disclosure
and is devoid of sigma phase precipitates;
[0029] FIG. 16A is a micrograph showing the microstructure at a mid-
radius of an alloy of Example 6 of the present disclosure that was forged and
cooled for a time that exceeded the calculated critical cooling time according
to the
present disclosure and exhibits sigma phase precipitates at the grain
boundaries;
[0030] FIG. 16B is a micrograph showing the microstructure at a mid-
radius of an alloy of Example 6 of the present disclosure that was forged and
cooled for a time within the calculated critical cooling time according to the
present
disclosure and does not exhibit sigma phase precipitates at the grain
boundaries;
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[0031] FIG. 17A is a micrograph showing the microstructure of a surface
region of an alloy of Example 7 of the present disclosure that was forged and
cooled for a time within the calculated critical cooling time according to the
present
disclosure and then warm worked without exhibiting sigma phase precipitates at
the grain boundaries; and
[0032] FIG. 17B is a micrograph showing the microstructure of a center
region of an alloy of Example 7 of the present disclosure that was forged and
cooled for a time within the calculated critical cooling time according to the
present
disclosure and then warm worked without exhibiting sigma phase precipitates at
the grain boundaries.
[0033] The reader will appreciate the foregoing details, as well as others,
upon considering the following detailed description of certain non-limiting
embodiments according to the present disclosure.
DETAILED DESCRIPTION OF CERTAIN NON-LIMITING EMBODIMENTS
[0034] It is to be understood that certain descriptions of the embodiments
described herein have been simplified to illustrate only those elements,
features, and
aspects that are relevant to a clear understanding of the disclosed
embodiments,
while eliminating, for purposes of clarity, other elements, features, and
aspects.
Persons having ordinary skill in the art, upon considering the present
description of
the disclosed embodiments, will recognize that other elements and/or features
may
be desirable in a particular implementation or application of the disclosed
embodiments. However, because such other elements and/or features may be
readily ascertained and implemented by persons having ordinary skill in the
art upon
considering the present description of the disclosed embodiments, and are
therefore
not necessary for a complete understanding of the disclosed embodiments, a
description of such elements and/or features is not provided herein. As such,
it is to
be understood that the description set forth herein is merely exemplary and
illustrative of the disclosed embodiments and is not intended to limit the
scope of the
invention as defined solely by the claims.
7
[0035] Also, any numerical range recited herein is intended to include
all sub-ranges subsumed therein. For example, a range of "1 to 10" is
intended to include all sub-ranges between (and including) the recited
minimum value of 1 and the recited maximum value of 10, that is, having a
minimum value equal to or greater than 1 and a maximum value of equal to or
less than 10. Any maximum numerical limitation recited herein is intended to
include all lower numerical limitations subsumed therein and any minimum
numerical limitation recited herein is intended to include all higher
numerical
limitations subsumed therein. Accordingly, Applicants reserve the right to
amend the present disclosure, including the claims, to expressly recite any
sub-range subsumed within the ranges expressly recited herein. All such
ranges are intended to be inherently disclosed herein such that amending to
expressly recite any such sub-ranges would comply with the requirements of
35 U.S.C. 112, first paragraph, and 35 U.S.C. 132(a).
[0036] The grammatical articles "one", "a", "an", and "the", as used
herein, are intended to include "at least one" or "one or more", unless
otherwise indicated. Thus, the articles are used herein to refer to one or
more
than one (i.e., to at least one) of the grammatical objects of the article. By
way
of example, "a component" means one or more components, and thus,
possibly, more than one component is contemplated and may be employed or
used in an implementation of the described embodiments.
[0037] All percentages and ratios are calculated based on the total
weight of the alloy composition, unless otherwise indicated.
[0038] Cancelled
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[0039] The present disclosure includes descriptions of various
embodiments. It is to be understood that all embodiments described herein are
exemplary, illustrative, and non-limiting. Thus, the invention is not limited
by the
description of the various exemplary, illustrative, and non-limiting
embodiments.
Rather, the invention is defined solely by the claims, which may be amended to
recite any features expressly or inherently described in or otherwise
expressly or
inherently supported by the present disclosure.
[0040] As used herein, the terms "forming", "forging", and "radial forging"
refer to forms of thermomechanical processing ("TMP"), which also may be
referred
to herein as "thermomechanical working". Thermomechanical working is defined
herein as generally covering a variety of metal forming processes combining
controlled thermal and deformation treatments to obtain synergistic effects,
such as
improvement in strength, without loss of toughness. This definition of
thermomechanical working is consistent with the meaning ascribed in, for
example,
ASM Materials Engineering Dictionary, J.R. Davis, ed., ASM International
(1992), p.
480.
[0041] Conventional alloys used in chemical processing, mining, and/or oil
and gas applications may lack an optimal level of corrosion resistance and/or
an
optimal level of one or more mechanical properties. Various embodiments of the
alloys processed as discussed herein may have certain advantages over
conventional alloys, including, but not limited to, improved corrosion
resistance
and/or mechanical properties. Certain embodiments of alloys processed as
described herein may exhibit one or more improved mechanical properties
without
any reduction in corrosion resistance, for example. Certain embodiments may
exhibit improved impact properties, weldability, resistance to corrosion
fatigue,
galling resistance, and/or hydrogen embrittlement resistance relative to
certain
conventional alloys.
[0042] In various embodiments, alloys processed as described herein may
exhibit enhanced corrosion resistance and/or advantageous mechanical
properties
suitable for use in demanding applications. Without wishing to be bound to any
particular theory, it is believed that certain of the alloys processed as
described
herein may exhibit higher tensile strength, for example, due to an improved
response
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to strain hardening from deformation, while also retaining high corrosion
resistance.
Strain hardening or cold working may be used to harden materials that do not
generally respond well to heat treatment. A person skilled in the art,
however, will
appreciate that the exact nature of the cold worked structure may depend on
the
material, applied strain, strain rate, and/or temperature of the deformation.
Without
wishing to be bound to any particular theory, it is believed that strain
hardening an
alloy having the composition described herein may more efficiently produce an
alloy
exhibiting improved corrosion resistance and/or mechanical properties than
certain
conventional alloys.
[0043] In certain non-limiting embodiments, the composition of an austenitic
alloy processed by a method according to the present disclosure comprises,
consists essentially of, or consists of, chromium, cobalt, copper, iron,
manganese,
molybdenum, nickel, carbon, nitrogen, tungsten, and incidental impurities. In
certain non-limiting embodiments, the austenitic alloy may, but need not,
include
one or more of aluminum, silicon, titanium, boron, phosphorus, sulfur,
niobium,
tantalum, ruthenium, vanadium, and zirconium, either as trace elements or as
incidental impurities.
[0044] Also, according to various non-limiting embodiments, the
composition of an austenitic alloy processed by a method of the present
disclosure
comprises, consists essentially of, or consists of, in weight percentages
based on
total alloy weight, up to 0.2 carbon, up to 20 manganese, 0.1 to 1.0 silicon,
14.0 to
28.0 chromium, 15.0 to 38.0 nickel, 2.0 to 9.0 molybdenum, 0.1 to 3.0 copper,
0.08
to 0.9 nitrogen, 0.1 to 5.0 tungsten, 0.5 to 5.0 cobalt, up to 1.0 titanium,
up to 0.05
boron, up to 0.05 phosphorus, up to 0.05 sulfur, iron, and incidental
impurities.
[0045] In addition, according to various non-limiting embodiments, the
composition of an austenitic alloy processed by a method according to the
present
disclosure comprises, consists essentially of, or consists of, in weight
percentages
based on total alloy weight, up to 0.05 carbon, 1.0 to 9.0 manganese, 0.1 to
1.0
silicon, 18.0 to 26.0 chromium, 19.0 to 37.0 nickel, 3.0 to 7.0 molybdenum,
0.4 to 2.5
copper, 0.1 to 0.55 nitrogen, 0.2 to 3.0 tungsten, 0.8 to 3.5 cobalt, up to
0.6 titanium,
a combined weight percentage of niobium and tantalum no greater than 0.3, up
to
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0.2 vanadium, up to 0.1 aluminum, up to 0.05 boron, up to 0.05 phosphorus, up
to
0.05 sulfur, iron, and incidental impurities.
[0046] Also, according to various non-limiting embodiments, the
composition of an austenitic alloy processed by a method according to the
present
disclosure may comprise, consist essentially of, or consist of, in weight
percentages
based on total alloy weight, up to 0.05 carbon, 2.0 to 8.0 manganese, 0.1 to
0.5
silicon, 19.0 to 25.0 chromium, 20.0 to 35.0 nickel, 3.0 to 6.5 molybdenum,
0.5 to 2.0
copper, 0.2 to 0.5 nitrogen, 0.3 to 2.5 tungsten, 1.0 to 3.5 cobalt, up to 0.6
titanium, a
combined weight percentage of niobium and tantalum no greater than 0.3, up to
0.2
vanadium, up to 0.1 aluminum, up to 0.05 boron, up to 0.05 phosphorus, up to
0.05
sulfur, iron, and incidental impurities.
[0047] In various non-limiting embodiments, the composition of an austenitic
alloy processed by a method according to the present disclosure comprises
carbon
in any of the following weight percentage ranges: up to 2.0; up to 0.8; up to
0.2; up
to 0.08; up to 0.05; up to 0.03; 0.005 to 2.0; 0.01 to 2.0; 0.01 to 1.0; 0.01
to 0.8; 0.01
to 0.08; 0.01 to 0.05; and 0.005 to 0.01.
[0048] In various non-limiting embodiments, the composition of an alloy
according to the present disclosure may comprise manganese in any of the
following
weight percentage ranges: up to 20.0; up to 10.0; 1.0 to 20.0; 1.0 to 10; 1.0
to 9.0;
2.0 to 8.0; 2.0 to 7.0; 2.0 to 6.0; 3.5 to 6.5; and 4.0 to 6Ø
[0049] In various non-limiting embodiments, the composition of an austenitic
alloy processed by a method according to the present disclosure comprises
silicon in
any of the following weight percentage ranges: up to 1.0; 0.1 to 1.0; 0.5 to
1.0; and
0.1 to 0.5.
[0050] In various non-limiting embodiments, the composition of an austenitic
alloy processed by a method according to the present disclosure comprises
chromium in any of the following weight percentage ranges: 14.0 to 28.0; 16.0
to
25.0; 18.0 to 26; 19.0 to 25.0; 20.0 to 24.0; 20.0 to 22.0; 21.0 to 23.0; and
17.0 to
21Ø
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[0051] In various non-limiting embodiments, the composition of an austenitic
alloy processed by a method according to the present disclosure comprises
nickel in
any of the following weight percentage ranges: 15.0 to 38.0; 19.0 to 37.0;
20.0 to
35.0; and 21.0 to 32Ø
[0052] In various non-limiting embodiments, the composition of an austenitic
alloy processed by a method according to the present disclosure comprises
molybdenum in any of the following weight percentage ranges: 2.0 to 9.0; 3.0
to 7.0;
3.0 to 6.5; 5.5 to 6.5; and 6.0 to 6.5.
[0053] In various non-limiting embodiments, the composition of an austenitic
alloy processed by a method according to the present disclosure comprises
copper
in any of the following weight percentage ranges: 0.1 to 3.0; 0.4 to 2.5; 0.5
to 2.0;
and 1.0 to 1.5.
[0054] In various non-limiting embodiments, the composition of an austenitic
alloy processed by a method according to the present disclosure comprises
nitrogen
in any of the following weight percentage ranges: 0.08 to 0.9; 0.08 to 0.3;
0.1 to
0.55; 0.2 to 0.5; and 0.2 to 0.3. In certain embodiments, nitrogen in the
austenitic
alloy may be limited to 0.35 weight percent or 0.3 weight percent to address
its
limited solubility in the alloy.
[0055] In various non-limiting embodiments, the composition of an austenitic
alloy processed by a method according to the present disclosure comprises
tungsten
in any of the following weight percentage ranges: 0.1 to 5.0; 0.1 to 1.0; 0.2
to 3.0;
0.2 to 0.8; and 0.3 to 2.5.
[0056] In various non-limiting embodiments, the composition of an austenitic
alloy processed by a method according to the present disclosure comprises
cobalt in
any of the following weight percentage ranges: up to 5.0; 0.5 to 5.0; 0.5 to
1.0; 0.8 to
3.5; 1.0 to 4.0; 1.0 to 3.5; and 1.0 to 3Ø In certain embodiments, cobalt
unexpectedly improved mechanical properties of the alloy. For example, in
certain
embodiments of the alloy, additions of cobalt may provide up to a 20% increase
in
toughness, up to a 20% increase in elongation, and/or improved corrosion
resistance. Without wishing to be bound to any particular theory, it is
believed that
replacing iron with cobalt may increase the resistance to deleterious sigma
phase
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precipitation in the alloy after hot working relative to non-cobalt bearing
variants
which exhibited higher levels of sigma phase at the grain boundaries after hot
working.
[0057] In various non-limiting embodiments, the composition of an
austenitic alloy processed by a method according to the present disclosure
comprises a cobalt/tungsten weight percentage ratio of from 2:1 to 5:1, or
from 2:1 to
4:1. In certain embodiments, for example, the cobalt/tungsten weight
percentage
ratio may be about 4:1. The use of cobalt and tungsten may impart improved
solid
solution strengthening to the alloy.
[0058] In various non-limiting embodiments, the composition of an austenitic
alloy processed by a method according to the present disclosure comprises
titanium
in any of the following weight percentage ranges: up to 1.0; up to 0.6; up to
0.1; up
to 0.01; 0.005 to 1.0; and 0.1 to 0.6.
[0059] In various non-limiting embodiments, the composition of an austenitic
alloy processed by a method according to the present disclosure comprises
zirconium in any of the following weight percentage ranges: up to 1.0; up to
0.6; up
to 0.1; up to 0.01; 0.005 to 1.0; and 0.1 to 0.6.
[0060] In various non-limiting embodiments, the composition of an austenitic
alloy processed by a method according to the present disclosure comprises
niobium
and/or tantalum in any of the following weight percentage ranges: up to 1.0;
up to
0.5; up to 0.3; 0.01 to 1.0; 0.01 to 0.5; 0.01 to 0.1; and 0.1 to 0.5.
[0061] In various non-limiting embodiments, the composition of an austenitic
alloy processed by a method according to the present disclosure comprises a
combined weight percentage of niobium and tantalum in any of the following
ranges:
up to 1.0; up to 0.5; up to 0.3; 0.01 to 1.0; 0.01 to 0.5; 0.01 to 0.1; and
0.1 to 0.5.
[0062] In various non-limiting embodiments, the composition of an austenitic
alloy processed by a method according to the present disclosure comprises
vanadium in any of the following weight percentage ranges: up to 1.0; up to
0.5; up
to 0.2; 0.01 to 1.0; 0.01 to 0.5; 0.05 to 0.2; and 0.1 to 0.5.
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[0063] In various non-limiting embodiments, the composition of an austenitic
alloy processed by a method according to the present disclosure comprises
aluminum in any of the following weight percentage ranges: up to 1.0; up to
0.5; up
to 0.1; up to 0.01; 0.01 to 1.0; 0.1 to 0.5; and 0.05 to 0.1.
[0064] In various non-limiting embodiments, the composition of an austenitic
alloy processed by a method according to the present disclosure comprises
boron in
any of the following weight percentage ranges: up to 0.05; up to 0.01; up to
0.008;
up to 0.001; up to 0.0005.
[0065] In various non-limiting embodiments, the composition of an austenitic
alloy processed by a method according to the present disclosure comprises
phosphorus in any of the following weight percentage ranges: up to 0.05; up to
0.025; up to 0.01; and up to 0.005.
[0066] In various non-limiting embodiments, the composition of an austenitic
alloy processed by a method according to the present disclosure comprises
sulfur in
any of the following weight percentage ranges: up to 0.05; up to 0.025; up to
0.01;
and up to 0.005.
[0067] In various non-limiting embodiments, the balance of the composition
of an austenitic alloy according to the present disclosure may comprise,
consist
essentially of, or consist of iron and incidental impurities. In various non-
limiting
embodiments, the composition of an austenitic alloy processed by a method
according to the present disclosure comprises iron in any of the following
weight
percentage ranges: up to 60; up to 50; 20 to 60; 20 to 50; 20 to 45; 35 to 45;
30 to
50; 40 to 60; 40 to 50; 40 to 45; and 50 to 60.
[0068] In various non-limiting embodiments, the composition of an austenitic
alloy processed by a method according to the present disclosure comprises one
or
more trace elements. As used herein, "trace elements" refers to elements that
may
be present in the alloy as a result of the composition of the raw materials
and/or the
melting method employed and which are present in concentrations that do not
significantly negatively affect important properties of the alloy, as those
properties
are generally described herein. Trace elements may include, for example, one
or
more of titanium, zirconium, niobium, tantalum, vanadium, aluminum, and boron
in
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any of the concentrations described herein. In certain non-limiting
embodiments,
trace elements may not be present in alloys according to the present
disclosure. As
is known in the art, in producing alloys, trace elements typically may be
largely or
wholly eliminated by selection of particular starting materials and/or use of
particular
processing techniques. In various non-limiting embodiments, the composition of
an
austenitic alloy according to the present disclosure may comprise a total
concentration of trace elements in any of the following weight percentage
ranges: up
to 5.0; up to 1.0; up to 0.5; up to 0.1; 0.1 to 5.0; 0.1 to 1.0; and 0.1 to
0.5.
[0069] In various non-limiting embodiments, the composition of an austenitic
alloy processed by a method according to the present disclosure comprises a
total
concentration of incidental impurities in any of the following weight
percentage
ranges: up to 5.0; up to 1.0; up to 0.5; up to 0.1; 0.1 to 5.0; 0.1 to 1.0;
and 0.1 to 0.5.
As generally used herein, the term "incidental impurities" refers to elements
present
in the alloy in minor concentrations. Such elements may include one or more of
bismuth, calcium, cerium, lanthanum, lead, oxygen, phosphorus, ruthenium,
silver,
selenium, sulfur, tellurium, tin, and zirconium. In various non-limiting
embodiments,
individual incidental impurities in the composition of an austenitic alloy
processed
according to the present disclosure do not exceed the following maximum weight
percentages: 0.0005 bismuth; 0.1 calcium; 0.1 cerium; 0.1 lanthanum; 0.001
lead;
0.01 tin, 0.01 oxygen; 0.5 ruthenium; 0.0005 silver; 0.0005 selenium; and
0.0005
tellurium. In various non-limiting embodiments, the composition of an
austenitic alloy
processed by a method according to the present disclosure, the combined weight
percentage of cerium, lanthanum, and calcium present in the alloy (if any is
present)
may be up to 0.1. In various non-limiting embodiments, the combined weight
percentage of cerium and/or lanthanum present in the composition of an
austenitic
alloy may be up to 0.1. Other elements that may be present as incidental
impurities
in the composition of austenitic alloys processed as described herein will be
apparent to those having ordinary skill in the art. In various non-limiting
embodiments, the composition of an austenitic alloy processed by a method
according to the present disclosure comprises a total concentration of trace
elements
and incidental impurities in any of the following weight percentage ranges: up
to
10.0; up to 5.0; up to 1.0; up to 0.5; up to 0.1; 0.1 to 10.0; 0.1 to 5.0; 0.1
to 1.0; and
0.1 to 0.5.
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[0070] In various non-limiting embodiments, an austenitic alloy processed
according to a method of the present disclosure may be non-magnetic. This
characteristic may facilitate use of the alloy in applications in which non-
magnetic
properties are important. Such applications include, for example, certain oil
and gas
drill string component applications. Certain non-limiting embodiments of the
austenitic alloy processed as described herein may be characterized by a
magnetic
permeability value (p.r) within a particular range. In various non-limiting
embodiments, the magnetic permeability value of an alloy processed according
to
the present disclosure may be less than 1.01, less than 1.005, and/or less
than
1.001. In various embodiments, the alloy may be substantially free from
ferrite.
[0071] In various non-limiting embodiments, an austenitic alloy processed
by a method according to the present disclosure may be characterized by a
pitting
resistance equivalence number (PREN) within a particular range. As is
understood, the PREN ascribes a relative value to an alloy's expected
resistance to
pitting corrosion in a chloride-containing environment. Generally, alloys
having a
higher PREN are expected to have better corrosion resistance than alloys
having a
lower PREN. One particular PREN calculation provides a PREN16 value using the
following formula, wherein the percentages are weight percentages based on
total
alloy weight:
PREN16 = %Cr + 3.3(%Mo) + 16(%N) + 1.65(%W)
In various non-limiting embodiments, an alloy processed using a method
according
to the present disclosure may have a PREN16 value in any of the following
ranges:
up to 60; up to 58; greater than 30; greater than 40; greater than 45; greater
than
48; 30 to 60; 30 to 58; 30 to 50; 40 to 60; 40 to 58; 40 to 50; and 48 to 51.
Without
wishing to be bound to any particular theory, it is believed that a higher
PREN16
value may indicate a higher likelihood that the alloy will exhibit sufficient
corrosion
resistance in environments such as, for example, in highly corrosive
environments,
that may exist in, for example, chemical processing equipment and the down-
hole
environment to which a drill string is subjected in oil and gas drilling
applications.
Aggressively corrosive environments may subject an alloy to, for example,
alkaline
compounds, acidified chloride solutions, acidified sulfide solutions,
peroxides, and/or
CO2, along with extreme temperatures.
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[0072] In various non-limiting embodiments, an austenitic alloy processed
by a method according to the present disclosure may be characterized by a
coefficient of sensitivity to avoid precipitations value (CP) within a
particular range.
The concept of a CP value is described in, for example, U.S. Patent No.
5,494,636,
entitled "Austenitic Stainless Steel Having High Properties". In general, the
CP
value is a relative indication of the kinetics of precipitation of
intermetallic phases in
an alloy. A CP value may be calculated using the following formula, wherein
the
percentages are weight percentages based on total alloy weight:
CP = 20(%Cr) + 0.3(%Ni) + 30(%Mo) + 5(%W) + 10(%Mn) + 50(%C) - 200(%N)
Without wishing to be bound to any particular theory, it is believed that
alloys
having a CP value less than 710 will exhibit advantageous austenite stability
which
helps to minimize HAZ (heat affected zone) sensitization from intermetallic
phases
during welding. In various non-limiting embodiments, an alloy processed as
described herein may have a CP in any of the following ranges: up to 800; up
to
750; less than 750; up to 710; less than 710; up to 680; and 660-750.
[0073] In various non-limiting embodiments, an austenitic alloy according to
the present disclosure may be characterized by a Critical Pitting Temperature
(CPT)
and/or a Critical Crevice Corrosion Temperature (CCCT) within particular
ranges. In
certain applications, CPT and CCCT values may more accurately indicate
corrosion
.. resistance of an alloy than the alloy's PREN value. CPT and CCCT may be
measured according to ASTM G48-11, entitled "Standard Test Methods for Pitting
and Crevice Corrosion Resistance of Stainless Steels and Related Alloys by Use
of
Ferric Chloride Solution". In various non-limiting embodiments, the CPT of an
alloy
processed according to the present disclosure may be at least 45 C, or more
preferably is at least 50 C, and the CCCT may be at least 25 C, or more
preferably
is at least 30 C.
[0074] In various non-limiting embodiments, an austenitic alloy processed
by a method according to the present disclosure may be characterized by a
Chloride
Stress Corrosion Cracking Resistance (SCC) value within a particular range.
The
.. concept of an SCC value is described in, for example, A. J. Sedricks,
Corrosion of
Stainless Steels (J. Wiley and Sons 1979). In various non-limiting
embodiments, the
SCC value of an alloy according to the present disclosure may be determined
for
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particular applications according to one or more of the following: ASTM G30-97
(2009), entitled "Standard Practice for Making and Using U-Bend Stress-
Corrosion
Test Specimens"; ASTM G36-94 (2006), entitled "Standard Practice for
Evaluating
Stress-Corrosion-Cracking Resistance of Metals and Alloys in a Boiling
Magnesium
Chloride Solution"; ASTM G39-99 (2011), "Standard Practice for Preparation and
Use of Bent-Beam Stress-Corrosion Test Specimens"; ASTM G49-85 (2011),
"Standard Practice for Preparation and Use of Direct Tension Stress-Corrosion
Test
Specimens"; and ASTM G123-00 (2011), "Standard Test Method for Evaluating
Stress-Corrosion Cracking of Stainless Alloys with Different Nickel Content in
Boiling
Acidified Sodium Chloride Solution." In various non-limiting embodiments, the
SCC
value of an alloy processed according to the present disclosure is high enough
to
indicate that the alloy can suitably withstand boiling acidified sodium
chloride
solution for 1000 hours without experiencing unacceptable stress corrosion
cracking,
pursuant to evaluation under ASTM G123-00 (2011).
[0075] It was discovered that the microstructures of forged workpieces of
alloy compositions described above may contain deleterious intermetallic
precipitates. It is believed that the intermetallic precipitates likely are
sigma phase
precipitates, i.e., (Fe,Ni)3(Cr,Mo)2 cornpounds. Intermetallic precipitates
may
impair corrosion resistance of the alloys and negatively impact their
suitability for
service in oil and gas drilling and other aggressive environments. FIG. 1
shows an
example of deleterious intermetallic precipitates 12 in the microstructure 10
at the
mid radius of a radial forged workpiece. The chemical composition of the alloy
shown in FIG. 1 falls within alloy compositions listed herein and consisted
of, in
weight percentages based on total alloy weight: 26.0397 iron; 33.94 nickel;
22.88
chromium; 6.35 molybdenum; 4.5 manganese; 3.35 cobalt; 1.06 tungsten; 1.15
copper; 0.01 niobium; 0.26 silicon; 0.04 vanadium; 0.019 carbon; 0.0386
nitrogen;
0.015 phosphorus; 0.0004 sulfur; and incidental impurities.
[0076] If intermetallic precipitates are confined to an alloy surface, surface
grinding can be used to remove the deleterious layer containing the
intermetallic
precipitates, with concomitant reduction in product yield and increase in
product
cost. In some alloy compositions, however, the deleterious intermetallic
precipitates may extend significantly into or throughout the cross-section of
a radial
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forged workpiece, in which case the workpiece may be wholly unsuitable in the
as-
radial forged condition for applications subjecting the alloy to, for example,
highly
corrosive conditions. An option for removing deleterious intermetallic
precipitates
from the microstructure is to solution treat the radial forged workpiece prior
to a
cooling temperature radial forging operation. This, however, adds an
additional
processing step and increases cost and cycle time. Additionally, the time it
takes
to cool the workpiece from the annealing temperature is dependent on the
diameter
of the workpiece, and it should be sufficiently rapid to prevent the formation
of the
deleterious intermetallic precipitates.
[0077] Without intending to be bound to any particular theory, it is believed
that the intermetallic precipitates principally form because the precipitation
kinetics
are sufficiently rapid to permit precipitation to occur during the time taken
to forge
the workpiece. FIG. 2 is an isothermal transformation curve 20, also known as
a
"TTT diagram" or "TTT curve", which predicts the kinetics for 0.1 weight
percent
a-phase (sigma phase) intermetallic precipitation in the alloy having the
composition described above for FIG. 1. It will be seen from FIG. 2 that
intermetallic precipitation occurs most rapidly, i.e., in the shortest time,
at the apex
22 or "nose" of the "C" curve that comprises the isothermal transformation
curve
20.
[0078] FIG. 3 is a graph showing a combination 30 of a calculated Center-
of-workpiece temperature 32, calculated mid-radius temperature 34, calculated
surface temperature 36, and actual temperatures from the radial forging of
experimental workpieces of austenitic alloys having the chemical compositions
listed in Table 1. These compositions fall within the scope of alloy
compositions
described above in the present detailed description. The workpieces had a
diameter of approximately 10 inches, and the actual temperatures were measured
using optical pyrometers. The temperature of the nose of the TTT diagram is
represented as line 38. Table 1 also shows the PREN116 values for the listed
alloy
compositions.
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Table 1
Element Heat 45FJ Heat 47FJ I Heat 48FJ Heat 49FJ
0.007 0.010 0.018 0.010
Mn 4,47 4,50 4.51 4.55
_______________ Cr 20.91 22.26 22.91 21,32
Mo 4,76 1 6.01 6.35 5.41
--------------- Co 2,05 2,60 3.38 2.01
Fe 40.67 32,37 26,20 39.57
Nb 0.01 0,01 0.01 0.01
NI 25.35 30.07 34.10 25,22
0.64 0.84 1.07 ---- 0.64
0.072 0,390 0,385 0.393
....
PRENie 44 50 52 47 --
[0079] It may be observed from FIG. 3 that the actual surface temperature
of the workpieces during radial forging is close to the temperature at which
the
kinetics of intermetallic precipitation are most rapid, thereby strongly
promoting
precipitation of the deleterious intermetallic compounds.
[0080] Using the thermodynamic modeling software JMatPro, available
from Sente Software Ltd., Surrey, United Kingdom, relationships were
determined
between the content of specific elements in certain alloys described herein
and (1)
the time to the apex of the isothermal transformation curve and (2) the
temperature
in the apex area of the isothermal transformation curve. It was determined
that
adjusting the levels of various elements in the alloys can change the time to
the
apex of the isothermal transformation curve and thereby permit
thermomechanical
processing to take place without the formation of the deleterious
intermetallic
precipitates. Examples of the thermomechanical processing that may be applied
include, but are not limited to, radial forging and press forging.
[0081] Accordingly, a non-limiting aspect of the present disclosure is
directed to a quantitative relationship discovered between the chemical
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composition of a high strength, non-magnetic austenitic steel and the maximum
allowable time for processing the alloy as it cools between a specific
temperature
range so as to avoid formation of deleterious intermetallic precipitates
within the
alloy. FIG. 4 is a ITT curve 48, showing a calculated sigma solvus temperature
42, a cooling temperature 44, and a critical cooling time 50, and also
illustrates a
relationship 40 according to the present disclosure defining the maximum time
or
critical cooling time 50 allowable for processing the alloy as it cools within
a specific
temperature range to avoid precipitation of deleterious intermetallics.
[0082] The relationship 40 illustrated in FIG. 4 may be described using
three equations. Equation 1 defines the calculated sigma solvus temperature,
represented in Fig. 4 by line 42.
Equation 1
Calculated Sigma SCAMS Temperature (T) 1155.8 - [(760.4).(%nickel I %iron)] +
[(1409)-(%chromium / %iron)] + [(2391.6).(%molybdenum / %iron)] -
[(288.9)-(%manganese / %iron) - [(634.8).(%cobalt / %iron)] +
[(107.8).(%tungsten / %iron)].
When austenitic steels according to the present disclosure are at or above the
calculated sigma solvus temperature according to Equation 1, the deleterious
intermetallic precipitates have not formed in the alloys.
[0083] In a non-limiting embodiment the workpiece is thermomechanically
processed at a temperature in a thermomechanical processing temperature range.
The temperature range is from a temperature just below the calculated sigma
solvus temperature 42 of the austenitic alloy to a cooling temperature 44 of
the
austenitic alloy. Equation 2 is used to calculate the cooling temperature 44
in
degrees Fahrenheit as a function of the chemical composition of the austenitic
steel
alloy. Referring to FIG. 4, the cooling temperature 44 calculated according to
Equation 2 is intended to predict the temperature of the apex 46 of the
isothermal
transformation curve 48 of the alloy.
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Equation 2
Coolina Temperature (T) = 1290.7 - [(604.2)-(%nickel / %iron)] +
[(829.6).(%chromium / %iron)] + [(1899.6)-(%molybdenum / %iron)] -
[(635.5).(%cobalt / %iron)] + [(1251.3).(%tungsten / %iron)].
[0084] Equation 3 is an equation that predicts the time in logio
minutes
at which the apex 46 of the isothermal transformation curve 48 for the
particular
alloy occurs.
Equation 3
Critical Cooling Time (log10 in minutes) = 2.948 + [(3.631).(%nickel / %iron)]
-
[(4.846).(%chromium / %iron)] - [(11.157)-(%molybdenum / %iron)] +
[(3.457)-(%cobalt I %iron)] - [(6.74).(%tungsten / %iron)].
[0085] Referring to FIG. 4, the time at which the apex 46 of the isothermal
transformation curve 48 occurs is represented by arrow 50. The time calculated
by
Equation 3 and represented by arrow 50 in FIG. 4 is referred to herein as the
"critical cooling time". If the time during which the alloy cools in
temperature range
that spans a temperature just below the calculated sigma solvus temperature 42
to
the cooling temperature 44 is longer than the critical cooling time 50,
deleterious
intermetallic precipitates may form. The intermetallic precipitates may render
the
alloy or product unsuitable for its intended use because of galvanic corrosion
cells
established between the intermetallic precipitates and the base alloy. More
generally, to prevent formation of deleterious intermetallic precipitates, the
time to
thermomechanically process the alloy in a temperature range spanning a
temperature just less than the calculated sigma solvus temperature 42 down to
the
cooling temperature 44 should be no greater than the critical cooling time 50.
[0086] In a non-limiting embodiment, the workpiece is allowed to cool from
a temperature just below the calculated sigma solvus temperature 42 to the
cooling
temperature 44 within a time no longer than the critical cooling time 50. It
will be
recognized that the workpiece can be allowed to cool during thermomechanical
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processing of the workpiece. For example, and not to be limiting, a workpiece
may
be heated to a temperature in a thermomechanical processing temperature range
and subsequently thermomechanically processed using a forging process. As the
workpiece is thermomechanically processed, the workpiece may cool to a degree.
In a non-limiting embodiment, allowing the workpiece to cool comprises the
natural
cooling that may occur during thermomechanical processing. According to an
aspect of the present disclosure, it is only required that the time that the
workpiece
spends in a cooling temperature range spanning a temperature just below the
calculated sigma solvus temperature 42 to the cooling temperature 44, is no
greater than the critical cooling time 50.
[0087] According to certain non-limiting embodiments, a critical cooling time
that is practical for forging, radial forging, or other thermomechanical
processing of
an austenitic alloy workpiece according to the present disclosure is within a
range of
10 minutes to 30 minutes. Certain other non-limiting embodiments include a
critical
cooling time of greater than 10 minutes, or greater than 30 minutes. It will
be
recognized that according to methods of the present disclosure, the critical
cooling
time calculated according to Equation 3 based on the chemical composition of
the
alloy is the maximum allowable time to thermomechanically process and/or cool
in a
temperature range spanning a temperature just less than the calculated sigma
solvus temperature (calculated by Equation 1 above) down to the cooling
temperature (calculated by Equation 2 above).
[0088] The calculated sigma solvus temperature calculated by Equation 1
and the cooling temperature calculated by Equation 2 define end points of the
temperature range over which the cooling time requirement, or, as referred to
herein,
the critical cooling time, is important. The time during which the alloy is
hot worked
at or above the calculated sigma solvus temperature calculated according to
Equation 1 is unimportant to the present method because elements forming the
deleterious intermetallic precipitates addressed herein remain in solution
when the
alloy is at or above the calculated sigma solvus temperature. Instead, only
the time
during which the workpiece is within the range of temperatures spanning a
temperature just less than the calculated sigma solvus temperature (calculated
using
Equation 1) to the cooling temperature (calculated using Equation 2), which is
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referred to herein as the cooling temperature range, is significant for
preventing
deleterious intermetallic a-phase precipitation. In order to prevent the
formation of
deleterious a-phase intermetallic particles, the actual time that the
workpiece spends
in the calculated cooling temperature range must be no greater than the
critical
cooling time as calculated in Equation 3.
[0089] Also, the time during which the workpiece is at a temperature below
the cooling temperature calculated according to Equation 2 is unimportant to
the
present method because below the cooling temperature, the rates of diffusion
of the
elements comprising the deleterious intermetallic precipitates are low enough
to
inhibit substantial formation of the precipitates. The total time it takes to
work the
alloy at a temperature less than the calculated sigma solvus temperature
according
to Equation 1 and then cool the alloy to the cooling temperature according to
Equation 2, Le, the time during which the alloy is in the temperature range
bounded
by (i) a temperature just less than the calculated sigma solvus temperature
and (ii)
.. the cooling temperature, must be no greater than the critical cooling time
according
to Equation 3.
[0090] Table 2 shows the calculated sigma solvus temperatures calculated
using Equation 1, the cooling temperatures calculated from Equation 2, and the
critical cooling times calculated from Equation 3 for the three alloys having
the
compositions in Table 1.
Table 2
Heat Heat Heat Heat
------------------------------------- 45FJ 47FJ 48FJ 49FJ
Calculated sigma solvus temperature CF) 1624 1774 1851 1694
Cooling temperature ( F) 1561 1634 1659 1600
Critical cooling time (min) 30A 10.5 8.0 166
[0091] According to a non-limiting aspect of the present disclosure,
thermomechanically working a workpiece according to methods of the present
disclosure comprises forging the workpiece. For the thermomechanical process
of
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forging, the thermomechanical working temperature and the thermomechanical
working temperature range according to the present disclosure may be referred
to as
the forging temperature and the forging temperature range, respectively.
[0092] According to another certain aspect of the present disclosure,
thermomechanically working a workpiece according to methods of the present
disclosure may comprise radial forging the workpiece. For the thermomechanical
process of radial forging, the thermomechanical processing temperature range
according to the present disclosure may be referred to as the radial forging
temperature range.
[0093] In a non-limiting embodiment of a method according to the present
disclosure, the step of thermomechanically working or processing the workpiece
comprises or consists of forging the alloy. Forging may include, but is not
limited to
any of the following types of forging: roll forging, swaging, cogging, open-
die
forging, closed-die forging, isothermal forging, impression-die forging, press
forging, automatic hot forging, radial forging, and upset forging. In a
specific
embodiment, forming comprises or consists of radial forging.
[0094] According to a non-limiting aspect of the present disclosure, a
workpiece may be annealed after steps of thermomechanical working and cooling
according to the present disclosure. Annealing comprises heating the workpiece
to
a temperature that is equal to or greater than the calculated sigma solvus
temperature according to Equation 1, and holding the workpiece at the
temperature
for period of time. The annealed workpiece is then cooled. Cooling the
annealed
workpiece in the temperature range spanning a temperature just below the
calculated sigma solvus temperature (calculated according to Equation 1) and
the
cooling temperature calculated according to Equation 2 must be completed
within
the critical cooling time calculated according to Equation 3 in order to
prevent
precipitation of the deleterious intermetallic phase. In a non-limiting
embodiment
the alloy is annealed at a temperature in a range of 1900 F to 2300 F, and the
alloy
is held at the annealing temperature for 10 minutes to 1500 minutes.
[0095] It will be recognized that the methods of processing an austenitic
alloy workpiece to inhibit precipitation of intermetallic compounds according
to the
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present disclosure apply to any and all of the alloys having chemical
compositions
described in the present disclosure.
[0096] FIG. 5 is a schematic diagram of a process 60 which is a non-
limiting embodiment of a method according to the present disclosure. Process
60
may be used to manufacture high strength non-magnetic steel product forms
having diameters useful for exploration and production drilling applications
in the oil
and gas industry. The material is melted to a 20-inch diameter ingot (62)
using a
combination of argon oxygen decarburization and electroslag remelting
(AOD/ESR). ROD and ESR are techniques known to those having ordinary skill
and, therefore, are not further described herein. The 20-inch diameter ingot
is
radial forged to 14-inch diameter (64), reheated, and radial forged to
approximately
9-inch diameter (66). The 9-inch diameter ingot is then allowed to cool (not
shown
in FIG. 5). The final step in the process 60 is a low temperature radial forge
operation reducing the diameter to approximately 7.25-inch diameter (68). The
7.25-inch diameter rod may be multiple cut (70) for polishing, testing, and/or
subsequent processing.
[0097] In the scheme shown in FIG. 5, the steps that pertain to the method
of the present disclosure are the step of radial forging the workpiece from
approximately 14-inch diameter (64) to approximately 9-inch diameter (66), and
the
.. subsequent or concurrent step during which the radial forged workpiece
cools (not
shown in FIG. 5). Referring to FIG. 4, all regions (i.e., the entire workpiece
cross-
section) of the radial forged approximately 9-inch diameter workpiece should
cool
from a temperature just below the calculated sigma solvus temperature 42 to
the
cooling temperature 44 in a time no greater than the calculated critical
cooling time
50. It will be recognized that in certain non-limiting embodiments according
to the
present disclosure, all or some amount of cooling to the cooling temperature
44 can
occur while the workpiece is simultaneously being thermomechanically worked or
forged, and the cooling of the workpiece need not occur entirely as a step
separate
from the thermomechanical working or forging step.
[0098] During a direct radial forging operation, the most rapid cooling
occurs at the surface of the workpiece, and the surface region may end up
being
processed at or below the cooling temperature 44 as described previously. To
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prevent the precipitation of the deleterious intermetallic precipitate, the
cooling time
of the surface region should conform to the constraint of the critical cooling
time 50
calculated from the alloy composition using Equation 3.
[0099] In a non-limiting embodiment, it is possible to shorten the available
cooling window by adding an additional process step aimed at eliminating the
intermetallic precipitate from the as-forged workpiece. The additional process
step
may be a heat treatment adapted to dissolve the intermetallic precipitate in
the as-
forged workpiece at temperatures greater than the calculated sigma solvus
temperature 42. However, any time taken for the surface, mid-radius, and
center of
the workpiece to cool after the heat treatment must be within the critical
cooling
time calculated according to Equation 3. The cooling rate after the additional
heat
treatment process step is partially dependent on the diameter of the
workpiece,
with the center of the workpiece cooling at the slowest rate. The greater the
diameter of the workpiece, the slower the cooling rate of the center of the
workpiece. In any case, cooling between a temperature just below the
calculated
sigma solvus temperature and the calculated cooling temperature should be no
longer than the critical cooling time of Equation 3.
[0100] An unexpected observation during the development of the present
invention was that nitrogen had a significant influence on the available time
for
processing in that the nitrogen suppressed precipitation of the deleterious
intermetallics and thereby permitted longer critical cooling times without
formation
of the deleterious intermetallics. Nitrogen, however, is not included in
Equations 1-
3 of the present disclosure because in a non-limiting embodiment, nitrogen is
added to the austenitic alloys processed according to the present methods at
the
element's solubility limit, which will be relatively constant over the range
of
chemical compositions for the austenitic alloys described herein.
[0101] After thermomechanically working an austenitic alloy and cooling
according to the methods herein and the constraints of Equations 1-3, the
processed
alloy may be fabricated into or included in various articles of manufacture.
The
articles of manufacture may include, but are not limited to, parts and
components for
use in the chemical, petrochemical, mining, oil, gas, paper products, food
processing, pharmaceutical, and/or water service industries. Non-limiting
examples
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of specific articles of manufacture that may include alloys processed by
methods
according to the present disclosure include: a pipe; a sheet; a plate; a bar;
a rod; a
forging; a tank; a pipeline component; piping, condensers, and heat exchangers
intended for use with chemicals, gas, crude oil, seawater, service water,
and/or
corrosive fluids (e.g., alkaline compounds, acidified chloride solutions,
acidified
sulfide solutions, and/or peroxides); filter washers, vats, and press rolls in
pulp
bleaching plants; service water piping systems for nuclear power plants and
power
plant flue gas scrubber environments; components for process systems for
offshore
oil and gas platforms; gas well components, including tubes, valves, hangers,
landing nipples, tool joints, and packers; turbine engine components;
desalination
components and pumps; tall oil distillation columns and packing; articles for
marine
environments, such as, for example, transformer cases; valves; shafting;
flanges;
reactors; collectors; separators; exchangers; pumps; compressors; fasteners;
flexible
connectors; bellows; chimney liners; flue liners; and certain drill string
components
such as, for example, stabilizers, rotary steerable drilling components, drill
collars,
integral blade stabilizers, stabilizer mandrels, drilling and measurement
tubulars,
measurements-while-drilling housings, logging-while-drilling housings, non-
magnetic
drill collars, non-magnetic drill pipe, integral blade non-magnetic
stabilizers, non-
magnetic flex collars, and compressive service drill pipe.
[0102] In connection with the methods according to the present disclosure,
the austenitic alloys having the compositions described in the present
disclosure
may be provided by any suitable conventional technique known in the art for
producing alloys. Such techniques include, for example, melt practices and
powder
metallurgy practices. Non-limiting examples of conventional melt practices
include,
without limitation, practices utilizing consumable melting techniques (e.g.,
vacuum
arc remelting (VAR) and ESR, non-consumable melting techniques (e.g., plasma
cold hearth melting and electron beam cold hearth melting), and a combination
of
two or more of these techniques. As known in the art, certain powdered
metallurgy
practices for preparing an alloy generally involve producing alloy powders by
the
following steps: AOD, vacuum oxygen decarburization (VOD), or vacuum induction
melting (VIM) ingredients to provide a melt having the desired composition;
atomizing the melt using conventional atomization techniques to provide an
alloy
powder; and pressing and sintering all or a portion of the alloy powder. In
one
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conventional atomization technique, a stream of the melt is contacted with the
spinning blade of an atomizer, which breaks up the stream into small droplets.
The
droplets may be rapidly solidified in a vacuum or inert gas atmosphere,
providing
small solid alloy particles.
[0103] After thermomechanically working and cooling a workpiece
according to the constraints of Equations 1-3 of the present disclosure, the
austenitic
alloys described herein may have improved corrosion resistance and/or
mechanical
properties relative to conventional alloys. After thermomechanically working
and
cooling a workpiece according to the constraints of Equations 1-3 of the
present
.. disclosure, non-limiting embodiments of the alloys described herein may
have
ultimate tensile strength, yield strength, percent elongation, and/or hardness
greater,
comparable to, or better than DATALLOY 2 alloy (UNS unassigned) and/or AL-
6XN alloy (UNS N08367), which are available from Allegheny Technologies
Incorporated, Pittsburgh, Pennsylvania USA. Also, after thermomechanically
.. processing and allowing the workpiece to cool according to the constraints
of
Equations 1-3 of the present disclosure, the alloys described herein may have
PREN, CP, CPT, CCCT, and/or SCC values comparable to or better than
DATALLOY 2 alloy and/or AL-6XN alloy. In addition, after thermomechanically
processing and allowing the workpiece to cool according to the constraints of
.. Equations 1-3 of the present disclosure, the alloys described herein may
have
improved fatigue strength, microstructural stability, toughness, thermal
cracking
resistance, pitting corrosion, galvanic corrosion, SCC, machinability, and/or
galling
resistance relative to DATALLOY 26 alloy and/or AL-6XN8 alloy. DATALLOY 28
alloy is a Cr-Mn-N stainless steel having the following nominal composition,
in weight
percentages: 0.03 carbon; 0.30 silicon; 15.1 manganese; 15.3 chromium; 2.1
molybdenum; 2.3 nickel; 0.4 nitrogen; balance iron and impurities. AL-6XN
alloy is
a superaustenitic stainless steel having the following typical composition, in
weight
percentages: 0.02 carbon; 0.40 manganese; 0.020 phosphorus; 0.001 sulfur; 20.5
chromium; 24.0 nickel; 6.2 molybdenum; 0.22 nitrogen; 0.2 copper; balance iron
and
impurities.
[0104] In certain non-limiting embodiments, after thermomechanically
working and cooling a workpiece according to the constraints of Equations 1-3
of the
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present disclosure, the alloys described herein may exhibit, at room
temperature,
ultimate tensile strength of at least 110 ksi, yield strength of at least 50
ksi, and/or
percent elongation of at least 15%. In various other non-limiting embodiments,
after
forming, forging, or radial forging and cooling according to the present
disclosure, the
alloys described herein may exhibit, in an annealed state and at room
temperature,
ultimate tensile strength in the range of 90 ksi to 150 ksi, yield strength in
the range
of 50 ksi to 120 ksi, and/or percent elongation in the range of 20% to 65%.
[010511 The examples that follow are intended to further describe certain
non-limiting embodiments, without restricting the scope of the present
disclosure.
Persons having ordinary skill in the art will appreciate that variations of
the following
examples are possible within the scope of the invention, which is defined
solely by
the claims.
EXAMPLE 1
[0106] FIG. 6 shows an example of a TTT diagram 80 for an alloy that has
a relatively short allowable critical cooling time as calculated using
Equation 3 of
the present disclosure. The chemical composition of the alloy that is the
subject of
FIG. 6 includes, in weight percentages: 26.04 iron; 33.94 nickel; 22.88
chromium;
6.35 molybdenum; 4.5 manganese; 3.35 cobalt; 1.06 tungsten; 1.15 copper; 0.01
niobium; 0.26 silicon; 0.04 vanadium; 0.019 carbon; 0.386 nitrogen; 0.015
phosphorus; and 0.0004 sulfur. For this alloy composition, the calculated
sigma
solvus temperature 82 calculated according to Equation 1 of the present
disclosure
is about 1859 F; the cooling temperature 84 calculated according to Equation 2
of
the present disclosure is about 1665 F; and the critical cooling time 86
calculated
according to Equation 3 of the present disclosure is about 7.5 minutes.
According
the present disclosure, in order to prevent precipitation of the deleterious
intermetallic phase, the workpiece must be thermomechanically processed and
allowed to cool when within the temperature range just less that 1859 F (i.e.,
the
calculated sigma solvus temperature calculated by Equation 1) down to 1665 F
(i.e., the cooling temperature calculated according to Equation 2) for no
longer than
7.5 minutes (i.e., the critical cooling time calculated according to Equation
3).
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[0107] FIG. 7 shows microstructures of the center of an as-forged 9-inch
diameter workpiece having the composition of Heat 48FJ as disclosed in Table
1.
The 9-inch workpiece was made as follows. A 20-inch diameter electroslag
remelted (ESR) ingot was homogenized at 2225 F, reheated to 2150 F, hot worked
on a radial forge to an approximately 14-inch workpiece, and air cooled. The
14 inch workpiece was reheated to 2200 F and hot worked on a radial forge to
about a 9-inch diameter workpiece, followed by water quenching. The relevant
actual cooling time, i.e., the time to forge and then cool within the
temperature
range just below the 1859 F calculated sigma solvus temperature calculated by
Equation 1 down to the 1665 F cooling temperature calculated by Equation 2,
was
greater than the 7.5 minute critical cooling time calculated by Equation 3
allowable
to avoid intermetallic precipitation of sigma phase. As predicted from
Equations 1-
3, the micrograph of FIG. 7 shows that the microstructure of the as-forged 9-
inch
diameter workpiece contained deleterious intermetallic precipitates, most
probably
sigma, at the grain boundaries.
EXAMPLE 2
[0108] FIG. 8 shows an example of a TTT diagram 90 for an alloy that has
a longer critical cooling time calculated using Equation 3 than the alloy of
FIG. 6.
The chemical composition of the alloy of FIG. 8 comprises, in weight
percentages:
39.78 iron; 25.43 nickel; 20.91 chromium; 4.78 molybdenum; 4.47 manganese;
2.06 cobalt; 0.64 tungsten; 1.27 copper; 0.01 niobium; 0.24 silicon; 0.04
vanadium;
0.0070 carbon; 0.37 nitrogen; 0.015 phosphorus; and 0.0004 sulfur. The
calculated sigma solvus temperature 92 for the alloy calculated according to
Equation 1 is about 1634 F; the cooling temperature 94 calculated according to
Equation 2 is about 1556 F; and the critical cooling time 96 calculated
according to
Equation 3 disclosure is about 28.3 minutes. According the method of the
present
disclosure, in order to prevent precipitation of the deleterious intermetallic
phase
within the alloy, the alloy must be formed and cooled when in the temperature
range spanning a temperature just below the calculated sigma solvus
temperature
(1634 F) down to the calculated cooling temperature (1556 F) for a time no
greater
than the calculated critical cooling time (28.3 minutes).
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[0109] FIG. 9 shows the microstructure of the mid radius of an as-forged
9-inch diameter workpiece of the alloy. The workpiece was made as follows. An
approximately 20-inch diameter ESR ingot of the alloy was homogenized at
2225 F, hot worked on a radial forge to about a 14-inch diameter workpiece,
and
air cooled. The cooled workpiece was reheated to 2200 F and hot worked on a
radial forge to about a 10-inch diameter workpiece, followed by water
quenching.
The relevant actual cooling time, i.e., the time for forging and cooling while
in the
temperature range spanning a temperature just below the calculated sigma
solvus
temperature calculated according to Equation 1 (1634 F) down to the cooling
temperature calculated according to Equation 2 (1556 F), was less than the
critical
cooling time calculated according to Equation 3 (28.3 minutes) allowed to
avoid
intermetallic precipitation of sigma phase. As predicted from Equations 1-3,
the
micrograph of FIG. 9 shows that the microstructure of the as-forged 9-inch
diameter workpiece did not contain deleterious intermetallic sigma phase
precipitates at the grain boundaries. The darkened areas at the grain
boundaries
are attributed to metallographic etching artifacts and do not represent grain
boundary precipitates.
EXAMPLE 3
[0110] Samples of the non-magnetic austenitic alloy of heat number 49FJ
(see Table 1) were provided. The alloy had a calculated sigma solvus
temperature
calculated according to Equation 1 of 1694 F. The alloy's cooling temperature
calculated according to Equation 2 was 1600 F. The time to the nose of the C
curve the TTT diagram (i.e., the critical cooling time) calculated according
to
Equation 3 was 15.6 minutes. The alloy samples were annealed at 1950 F for 0.5
hours. The annealed samples were placed in a gradient furnace with the back
wall
of the furnace at approximately 1600 F, the front wall of the furnace at
approximately 1000 F, and a gradient of intermediate temperatures within the
furnace between the front and back wall. The temperature gradient in the
furnace
is reflected in the plot depicted in FIG. 10. The samples were placed at
locations
within the furnace so as to be subjected to temperatures of 1080 F, 1200 F,
1300 F, 1400 F, 1500 F, or 1550 F, and were heated for 12 minutes, 50 minutes,
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hours, or 20 hours. The microstructure of each sample was evaluated at the
particular heating temperature applied to the sample.
[0111] FIG. Ills a TTT diagram with the heating temperature gradients
(horizontal lines) and the actual cooling times (vertical lines) that were
used in
5 these experiments. FIG. 12 superimposes microstructures from samples held
for
12 minutes at various temperatures on the TTT diagram. FIG. 13 superimposes
microstructures from samples held at 1080 F for various times on the TTT
diagram.
In general, the results confirm the accuracy of the TTT diagrams in that
precipitation of the intermetallic phase addressed herein occurred at
approximately
10 the temperatures and times defined by the TTT diagram.
EXAMPLE 4
[0112] A 20-inch diameter ESR ingot having the chemistry of Heat 48FJ
was provided. The alloy had a calculated sigma solvus temperature calculated
using Equation 1 of 1851 F. The cooling temperature calculated according to
Equation 2 was 1659 F. The time to the nose of the C curve the TTT diagram
(i.e.,
the critical cooling time) calculated according to Equation 3 was 8.0 minutes.
The
ESR ingot was homogenized at 2225 F, reheated to 2225 F and hot worked on a
radial forge to approximately a 14-inch diameter workpiece, and then air
cooled.
The cooled 14-inch diameter workpiece was reheated to 2225 F and hot worked on
a radial forge to approximately a 10-inch diameter workpiece, followed by
water
quenching. Optical temperature measurements during the radial forging
operation
indicated that the temperature at the surface was approximately 1778 F, and as
the
radial forged workpiece was entering the water quenching tank, the surface
temperature was about 1778 F. The radial forged and water quenched workpiece
was annealed at 2150 F and then water quenched.
[0113] FIG. 14A shows the microstructure at the surface of the annealed
radial forged workpiece. FIG. 14B shows the microstructure at the center of
the
annealed radial forged workpiece. The 2150 F annealing step solutionizes the
sigma phase that was formed during the radial forging operation. The
calculated
critical cooling time of 8.0 minutes, however, is insufficient to prevent
sigma phase
formation at the center of the ingot as the ingot cools from a temperature
just below
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the 1851 F calculated sigma solvus temperature to the 1659 F calculated
cooling
temperature during the water quenching operation. The photomicrograph of FIG.
14A shows that the surface cooled sufficiently rapidly to avoid sigma phase
precipitation, but the micrograph of FIG. 14B shows that cooling at the center
of the
ingot occurred slowly enough to permit precipitation of sigma phase. The
center of
the ingot cooled from the calculated sigma solvus temperature calculated by
Equation 1 to the cooling temperature calculated by Equation 2 in a time
period
greater than the critical cooling time calculated by Equation 3.
EXAMPLE 5
[0114] A 20-inch diameter ESR ingot having the chemistry of Heat 45FJ
was provided. The alloy had a calculated sigma solvus temperature calculated
using Equation 1 of 1624 F. The cooling temperature calculated according to
Equation 2 was 1561 F. The time to the nose of the C curve the TTT diagram (L
e . ,
the critical cooling time) was 30.4 minutes. The ESR ingot was homogenized at
2225 F, reheated to 2225 F and hot worked on a radial forge to approximately a
14
inch diameter workpiece, and then air cooled. The workpiece was reheated to
2225 F and hot worked on a radial forge to approximately a 10-inch diameter
workpiece, followed by water quenching. Optical temperature measurements
during the radial forging operation indicated that the workpiece surface
temperature
was approximately 1886 F, and as the radial forged workpiece was entering the
water quenching tank, the surface temperature was about 1790 F.
[0115] FIG. 15A shows the microstructure at the surface of the radial
forged and water quenched workpiece. FIG. 15B shows the microstructure at the
center of the radial forged and water quenched workpiece. The microstructures
shown in both FIG. 15A and FIG. 15B are devoid of sigma precipitation. This
confirms that the actual time to cool from a temperature just below the
calculated
sigma solvus temperature of 1624 F down to the calculated cooling temperature
of
1561 F was sufficiently quick (i.e., was less than 30.4 minutes) to avoid
precipitation of sigma phase at both the surface and the center of the radial
forged
and water quenched workpiece.
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EXAMPLE 6
[0116] A 20-inch diameter ESR ingot having the chemistry of Heat 48FJ
was provided. The Heat 48FJ alloy had a calculated sigma solvus temperature
calculated using Equation 1 of 1851 F. The cooling temperature calculated
according to Equation 2 was 1659 F. The time to the nose of the C curve of the
ITT diagram (i.e., the critical cooling time) calculated according to Equation
3 was
8.0 minutes. A second 20-inch diameter ESR ingot, having the chemistry of Heat
49FJ, was provided. The Heat 49FJ alloy had a calculated sigma solvus
temperature calculated using Equation 1 of 1694 F. The cooling temperature
calculated according to Equation 2 was 1600 F. The time to the nose of the C
curve of the TTT diagram (i.e., the critical cooling time) calculated
according to
Equation 3 was 15.6 minutes.
[0117] Both ingots were homogenized at 2225 F. The homogenized
ingots were reheated to 2225 F and hot worked on a radial forge to
approximately
14-inch diameter workpieces, followed by air cooling. Both cooled workpieces
were reheated to 2225 F and hot worked on a radial forge to approximately 10-
inch
diameter workpieces, followed by water quenching.
[0118] Optical temperature measurements during the radial forging
operation of the Heat 48FJ ingot indicated that the temperature at the surface
was
approximately 1877 F, and entering the water quenching tank, the surface
temperature was about 1778 F. FIG. 16A shows the center microstructure of the
alloy, which included sigma phase precipitates at the grain boundary.
[0119] Optical temperature measurements during the radial forging
operation of the Heat 49FJ ingot indicated that the temperature at the surface
was
approximately 1848 F, and entering the water quenching tank the surface
temperature was about 1757 F. FIG. 16B shows the center microstructure of the
alloy, which is devoid of sigma phase precipitates. Dark regions at the grain
boundaries in the micrograph of FIG. 16B are attributed to metallographic
etching
artifacts.
[0120] These results demonstrate that even when processed under
essentially identical conditions, the workpiece with the shorter critical
cooling time
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as calculated by Equation 3 (Heat 48FJ) developed sigma phase at its center,
whereas the workpiece with the longer critical cooling time (Heat 49FJ) as
calculated by Equation 3 did not develop sigma phase precipitates at its
center.
EXAMPLE 7
[0121] A 20-inch diameter ESR ingot having the chemistry of Heat 49FJ
was provided. The Heat 49FJ alloy had a calculated sigma solvus temperature
calculated using Equation 1 of 1694 F. The cooling temperature calculated
according to Equation 2 was 1600 F. The time to the nose of the C curve of the
ITT diagram (i.e., the critical cooling time) calculated according to Equation
3 was
15.6 minutes. The ingot was homogenized at 2225 F, reheated to 2225 F and hot
worked on a radial forge to approximately a 14-inch diameter workpiece, and
then
air cooled. The air cooled workpiece was reheated to 2150 F and hot worked on
a
radial forge to approximately a 9-inch diameter workpiece, followed by water
quenching. Optical temperature measurements during the radial forging
operation
indicated that the temperature at the surface was approximately 1800 F, and as
the
radial forged workpiece was entering the water quenching tank, the surface
temperature was about 1700 F. The forged and water quenched workpiece was
then reheated to 1025 F and warm worked on a radial forged to approximately a
7.25-inch diameter workpiece, followed by air cooling.
[0122] The microstructure of the surface of the 7.25-inch diameter
workpiece is shown in FIG. 17A, and the microstructure of the center of the
7.25-
inch diameter workpiece is shown in FIG. 17B. The micrographs show that there
was no sigma phase at either the surface or the center of the workpiece. In
this
example, the workpiece having the chemistry of Heat 49FJ was processed through
the relevant temperature range, i.e., the temperature range bounded by a
temperature just below the calculated sigma solvus temperature and down to the
calculated cooling temperature, in less than the calculated critical cooling
time,
thereby avoiding precipitation of sigma phase.
[0123] It will be understood that the present description illustrates those
aspects of the invention relevant to a clear understanding of the invention.
Certain
aspects that would be apparent to those of ordinary skill in the art and that,
therefore,
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would not facilitate a better understanding of the invention have not been
presented
in order to simplify the present description. Although only a limited number
of
embodiments of the present invention are necessarily described herein, one of
ordinary skill in the art will, upon considering the foregoing description,
recognize
that many modifications and variations of the invention may be employed. All
such
variations and modifications of the invention are intended to be covered by
the
foregoing description and the following claims.
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